After-fixing dyes with monoaminoalkylsilicones with aminoalkyl chainshaving 3 carbon atoms

ABSTRACT

IN A PROCESS FOR IMPROVING THE FASTNESS OF DYEINGS AND PRINTS ON PREVIOUSLY DYED AND PRINTED PRINTED SUBSTRATA SUCH SUBSTRATA HAVING BEEN DYED AND PRINTED WITH WATERSOLUBLE DIRECT DYESTUFFS, THE IMPROVEMENT THAT COMPRISES AFTER-TREATING THE SUBSTRATE TO DEPOSIT THEREON A COATING OF A DYE-FIXATIVE SELECTED FROM THE GROUP CONSISTNG OF AMINOALKYL SILICONES AND METAL COORDINATED COMPLEXES OF THE SAME SELECTED FROM THE GROUP CONSISTING OF MONOMERIC AMINOALKYLSILANES, AMINOALKYPOLYSILOXANES, COPOLYMERS OF AMINOALKYPOLYSILOXANES WITH AT LEAST ONE OTHER POLYSILOXANE, BLADE OF AMINOALKYLPOLYSILOXANES WITH AT LEAST ONE OTHER POLYSILOXANE AND METAL COORDINAED COMPLEXES OF SUCH AMINOALKUL SILICONES, SUCH AMINOALKYL SILICONE COLORING ASSISTANT CONTAINING AT LEAST ONE AMINO SUBSTITUENT WHEREIN THE NITROGEN ATOM OF THE AMINO GROUP IS CONNECTED TO A SILICON ATOM OF THE SILICONE DIRECRLY THROUGH A DIVALENT HYDROCARBON RADICAL AND THE AMINO NITROGEN IS SEPARATED BY AT LEAST THREE CARBON ATOMS FROM THE SILICON ATOM.

United States Patent lint. Cl. 1106p 5/02 U.S. Cl. 8-74 18 ClaimsABSTRACT OF THE DISCLOSURE In a process for improving the fastness ofdyeings and prints on previously dyed and printed printed substrata suchsubstrata having been dyed and printed with watersoluble directdyestuffs, the improvement that comprises after-treating the substrateto deposit thereon a coating of a dye-fixative selected from the groupconsisting of aminoalkyl silicones and metal coordinated complexes ofthe same selected from the group consisting of monomeric'aminoalkylsilanes, aminoalkylpolysiloxanes, copolymers ofaminoalkylpolysiloxanes with at least one other polysiloxane, blends ofaminoalkylpolysiloxanes with at least one other polysiloxane and metalcoordinated complexes of such aminoalkyl silicones, such aminoalkylsilicone coloring assistant containing at least one amino substituentwherein the nitrogen atom of the amino group is connected to a siliconatom of the silicone directly through a divalent hydrocarbon radical andthe amino nitrogen is separated by at least three carbon atoms from thesilicon atom.

This is a continuation of application Ser. No. 804,882, filed Apr. 8,1959 now Pat. No. 3,572,833.

The present invention relates, in general, to the chemistry of coloring,and involves the provision of improved processes for fixing colors onpreviously dyed or printed substrata of various types including, forexample, fibrous textile products, leather goods, and the like. Moreparticularly, the invention is concerned with both process and productimprovements resulting, in part, from my discovery that aminoalkylsilicon compounds and coordinated metal complexes of these compoundsconstitute a unique class of dye-fixatives which can be used in theaftertreatment of numerous substrate materials of both natural andsynthetic origin to promote enhanced overall fastness, and, notably,washfastness or insolubilization, of substantive dyestuffs containedthereon. The processes of the invention find specific application in theproduction of washfast substantive colors on cellulosic substratematerials of all types.

In general, the two most important properties of a dyestuff are itssubstantivity and overall fastness to removal and modification. Thesubstantivity of a dyestufi enables it to be exhausted from a dye bathor printing medium and transferred in uniform manner to a substrateundergoing coloring, whereas, once the dyestulf has been deposited onthe substrate, it is expected to remain thereon and not change to anyappreciable extent in intensity or shade under influence of factors suchas wash solutions, perspiration, rain, ironing, light, atmosphericcontaminants, etc., or, in sort, it must possess good fastness. Underordinary circumstances, i.e., in the absence of any form ofaftertreatment, the substantive dyestufi molecule is held to thesubstrate by the same forces or mechanism which enabled it to bedeposited or exhausted from the dye bath, and it is frequently foundthat these forces are inadequate to counteract the re-solution tendencyof the dyestutf when the colored substate is placed in aqueous solutionor aqueous soap and alkaline solutions. That is ice to say, theequilibrium of the system, water-dyestuff-substrate, is initially upsetor destroyed by the attracting forces acting between the substrate anddyestulf molecule during the dyeing or printing cycle, and it is obviousthat new conditions of equilibrium can set in when the colored substrateis again placed in aqueous solution, particularly in the presence ofcatalytic influences such as heat, soaps, alkaline agents, etc. In orderto insure that a soluble dyestulf (or the soluble derivative of aninsoluble dyestuff) will not be released to solution under theseconditions, or, in essence, to enhance the normal natural aflinity ofthe dyestuff for the substrate and thereby promote improved equilibriumfor the substrate-dyestulf system, it is often necessary or desirable,particularly with dyestuffs of the substantive classes, or when workingwith a coloring agent having insuflicient natural afiinity for aparticular substrate material, to subject the dyed or printed substrateto an aftertreatment with a suitable dyefixing agent.

Heretofore, a great many different types of dye-fixatives have beendeveloped and employed to varying extents by the textile and alliedcoloring industries. By way of illustration, formaldehyde, its urea andmelamine monomers, cationic softening agents and heavy metal salts havebeen shown to be effective in minimizing the bleeding of most textilesubstrates dyed with direct colors, whereas the washfastness of certainacetate dyeings can be enhanced through use of similar agents. Inaddition, it has been established that the washfastness of directdyeings and prints on rayon substrate materials are generally improvedthrough finishing treatments with metallic salts, such as zinc,magnesium or aluminum acetate, by use of cationic softening agents, andby use of cationic resinous copper complexes. Other cationic resinouscomplexes, such as the polyanthrenes, are used to produce washfastcolors on viscose substrata dyed with direct dyes, and, under certainconditions, these agents are reportedly capable of promoting someimprovement in the lightfastness of the direct colors.

While it is recognized that a great variety of dye-fixing agents havebeen developed heretofore, the most common forms of aftertreatmentpresently employed by industry to promote increased fastness of pre-dyedsubstrates include, finishing techniques involving use of theformaldehyde-type dye-fixatives; aftertreatments with metallic saltssuch as copper and chrome salts, or resinous copper complexes such ascopper coordinated base resins consisting of condensates of diethylenetriamine, triethylene tetramine, or tetraethylene pentamine withdicyandiamine; and, for amino-containing dye-stuffs, the application ofconventional diazotization and coupling mechanisms.

Since the fastness to light of a dyed substrate involves a photochemicalreaction which is largely dependent on the constitution of the dyestuffmolecule, per se, as distinguished from the dyestuff-substrate systeminvolved in the mechanism of washfastness, improvement in the formerproperty is not ordinarily sought by colorists through application ofseparate aftertreatment techniques. On the other hand, it commonlyoccurs that certain forms of conventional dye-fixatives intended forapplication to previously dyed substrate materials to induce improvedwashfastness of substantive colors, will actually decrease the normallightfastness characteristics of the dyestulf molecule. In a similarmanner, other commonly used dyefixing agents result in appreciable shadechanges or changes in the intensity of coloration of previously dyedsubstrata, such that the colorists must regulate the dyeing or printingcycle to provide for these changes.

The diazotization and coupling type of fastness treatment is based onthe ability of the dyestuff molecule to react with aromatic compoundscontaining activating groups, and, as such, is restricted in itsapplications to dyestuffs which contain at least one free primary ammogroup. The aftertreatment techniques involving use of copper salts havebeen found to be effective chiefly for increasing fastness of thedyestuff to light, whereas, the chromium salt-type of aftertreatmentincreases fastness to washings, but, in both instances, these types ofdye-fixing agent produce considerable change in the original shade ofdyed substrata. In the case of the formaldehyde fixatives, the chiefobjection to use of these agents stems from the characteristicformaldehyde odors which they impart to the dyed materials, and, in thesame manner, the commonly used amino resin dye-fixatives produceobjectionable fishy amine odors, and are not readily compatible for usewith other textile processing chemicals.

In contrast to the foregoing, I have found that the aminoalkyl siliconesand their coordinated metal complexes are extremely effective dyefixingagents, functioning, even at relatively low concentrations, toinsolubilize substantive dyestuffs contained on virtually any substratematerial, and serving to prevent bleeding, leaching, and washing-out ofthe dyestuffs under the most severe conditions or criteria ofwashfastness. The dye-fixatives of the invention are entirely compatiblewith most other textile processing chemicals, free of objectionableodors, capable of effecting fixation with substantially less shadechanges than are customarily encountered through use of conventionaldye-fixing agents, and further capable of imparting improved storagestability and greater durability to dyed substrata treated in accordancewith the general processing techniques of my invention.

Owing to their general physical properties, the aminoalkyl siliconedye-furatives can be applied as a Wet processing operation as, forexample, by exhaustion, following the usual dyeing or printing cycle, orthey can be applied from aqueous media as a finish on the dyed and driedsubstrata. The actual choice of procedures in this connection willdepend upon a number of factors peculiar to existing plant installationsand conventions, and to the particular characteristics of the dyestuffand substrate involved, including, by way of illustration, the physicalnature and form of the substrate, the recommended processing techniquesnormally required for most efficient utilization of the dyestuff, suchas post-drying cycles, etc., and the presence or absence of auxiliariesor other finishing agents within the overall dyeing and finishingoperations. While most dyeing or printing and finishing operations canbe suitably modified to permit application of either type ofaftertreatment, it is found to be most convenient to apply thedye-fixatives by Wet processing techniques immediately following thenormal dyeing or printing cycle.

In actual practice of the invention, I prefer to apply the aminoalkylsilicone dye-fixatives to colored substrate materials by a simpleimmersion operation within a suitable aqueous solution of the aminoalkylsilicone, but it is entirely possible, and practical, to accomplish thereq uisite loading by spraying or padding techniques or any other meansnormally used by industry. If necessary or desirable, the aminoalkylsilicone can be solubilized beyond its normal solubility in pure aqueoussolutions through use of acid, neutral or alkaline reagents, oremulsions of the dye-fixatives can be employed with entirelysatisfactory results. Enhanced solubilization of the aminoalkyl siliconedye-fixatives may also be effected by salt formation, or by directchemical modification of the base compounds to introduce solubilizinggroups, such as by hydroxy ethylation, and the like. Virtually anysolvent system which is substantially non-reactive with the aminoalkylsilicones can be employed to promote more uniform distribution ordispersion of the dye-fixative onto the dyed or printed substratematerials. In addition, most of the commercially available wettingagents normally in use within the dyeing and finishing industries can beemployed to further promote enhanced dispersion of the silicones.

Among the specific solvents which have been employed with success in thepractice of the invention are included the aliphatic oxygen-containingcompounds such as the akanols and the ether alcohols, such as ethanol,propanol, isopropanol, methoxyethanol, ethoxyethanol, and the like. Inaddition, monobasic acids such as formic, acetic and propionic acids areexcellent solubilizing agents for the aminoalkyl silicone dye-fixatives.Included as monobasic acids, such as, lactic acid, gluconic acid,glycolic acid, other hydroxy carboxylic acids are suitable for use assolubilizing agents and provide improved fixing properties. Othercarboxylic acids, such as, diglycolic acid, can be used. Mineral acidsmay also be employed as may the standard aromatic hydrocarbon solventssuch as benzene, toluene, xylene, and the like, but these solubilizingagents are not as preferred for general use as are the simple aqueoussystems or the aqueous-alcoholic and monobasic acid-modified solventsystems. Lastly, the dye-fixatives may also be deposited from aqueousalkaline solutions. In actual practice, I have found that an aqueoussystem comprised of from about 40 to 60 parts water and from about 40 to60 parts of an organic alcohol such as ethanol or isopropanol, andcontaining approximately five percent (5%) by volume of a monobasic acidsuch as acetic acid, provides an excellent medium for solubilizing anddispersing the aminoalkyl silicone dye-fixatives onto virtually any dyedor printed substrate material.

The concentration of the aminoalkyl silicone dyefixatives containedwithin the aftertreatment solutions is found to be relativelynon-critical from the standpoint of establishing good fastnessproperties for the substantive colors on various types of substrata.Thus, for example, as established by the experimental data presentedhereinafter, a decrease in solution concentration from an initial valueof 5% by Weight of aminoalkyl silicone solids to 1% by weight,representing a decrease of from 3.0% to 0.6% by weight of siliconesolids actually deposited from solution onto a previously direct-dyedtextile material, produced little or no change in the washfastnessproperties of the respective end-products. While the concentration ofthe dye-fixatives can be varied anyhwere within the range of from 0.1 to5.0% by weight, or higher, based on deposited silicone solids, it isfound that for most substantive dyestuffs good dye-fixing properties canbe produced at deposited solids concentrations within the range of from0.1 to 2.0% by weight, whereas concentrations of the order of from 0.1to 1.0% by weight are actually highly effective for many of thesubstantive dyestuffs. Ordinarily, the solution concentration of theaminoalkyl silicone solids is regulated in accordance with thepercentage wet pick-up characteristics for the particular dyed orprinted substrate material undergoing dye-fixing, which is dependent, inturn, on the relative hydrophilic or hydrophobic nature of the varioussubstrate materials. That is to say, by suitably adjusting the solutionconcentration in accordance with the wet pick-up characteristics for aparticular substrate undergoing treatment, it is relatively simple toadjust the aftertreatment solution to an optimum concentration ofsilicone solids for the dyestuffsubstrate system involved. These factorsare well known to experienced dyers and finishers who must adjust therelative concentrations of most known auxiliaries and finishing agentsto meet the exigencies of many varied coloring and finishing operations,and, accordingly, it is not believed to be necessary to comment furtheron such variables for purposes of this disclosure.

In the dye-fixing processes of the invention, it is desirable to effectforced drying of the aminoalkyl silicone deposits by heating thesubstrate material at an elevated temperature after it has been removedfrom the aftertreatment solution, or is otherwise processed to depositthe desired dye-fixative thereon, although simple air-dried substratahave also been dye-fixed to provide good washfastness properties. It isbelieved that such drying of the dyed or printed and aftertreatedsubstrate materials at elevated temperatures efiectively cures thedeposited silicone to the substrate, or, more concisely, the deposit isfixed or bonded to the substrate by the heating operation. In thisconnection, it should be stated that the exact mechanism or mechanismsof the dye-fixing phenomena of my invention are not fully understood,although it is believed that the aminoalkyl silicones form insolublecomplexes with the dyestulf molecules and/ or bonding of the dyestuff tothe substrate material. It is assumed, however, that the mechanisminvolves something more than simple surface coating, and that at leastlimited penetration, absorption, or depth of reaction, so to speak,occurs between the substrate-dyestuff system and the aminoalkyl siliconedye-fixatives. It should be understood, therefore, that the referencesto deposits" or coatings or applications as used herein and in theappended claims, having reference to the aminoalkyl siliconeaftertreatments, are not to be construed as limitations to a simplesurface or physical phenomenon.

Drying and curing of the aminoalkyl silicone deposits can be effected atroom temperature over protracted periods or by heating the treatedsubstrate materials at higher temperatures for relatively shorterperiods of time. Actually, time and temperature are inversely related inthe curing mechanism, such that it is entirely possible to eifect fiashcures within a matter of seconds, provided the particular substratematerial will withstand the higher temperatures required for such cures.In actual practice, however, I prefer to operate at curing temperatureswithin the range of from ZOO-350 F., over periods ranging anywhere froma few minutes to one-half hour, dependent on the particular wet pick-upcharacteristics of the colored substrate undergoing dye-fixing. When thedyefixing operation is effected by wet processing following the dyeingor printing cycle, the necessary drying and curing operations areadvantageously effected as an incident to the normal heating cyclesrequired for the dyeing or printing processes, but the heat treatmentcan be practiced as a separate step following completion of the normaldyeing or printing process.

Quite naturally, by reason of the fastness problems peculiar to suchdyeings and printings, the processes of the invention find particularcommercial application in the aftertreatment of cellulosic substratadyed with substantive dyestuffs. The dyeings or prints which may besubjected to the aftertreatment of the invention may be contained on anyfibrous material, however, including single filaments, yarns or fabricsand textiles from either staple or continuous fibers. Suitable commontextile materials and natural fibrous materials include substrata suchas cotton, linen, ramie, hemp, jute, wood pulp, paper, leather, furs,feathers, cellulose ethers, cellulose esters, e.g., cellulose acetateand cellulose, regenerated cellulose rayons produced by any process,e.g., viscose, cuprammonium, etc., natural silks, tussore silk, wool,and the like. In general, the dye-fixatives of the invention may beemployed to increase the fastness of any soluble dyestuff wherever usedin accordance with current coloring practices.

Apart from the foregoing conventional fixing applications, however, theprocesses of the invention may also be applied to effect enhancedfixation of dyestuffs on a great many other types of substrata which arecolored through use of coloring agents having relatively inferiornatural aifinity for the substrate involved. For example, in mycopending, US. application Ser. No. 804,870, filed on Apr. 8, 1959, Ihave described and claimed processes which are based on the uniquecolor-affinity, for pigments of both natural and synthetic origin aswell as anionic dyestuffs, that can be impartedthrough pre-treatmentwith, and/or concurrent use within the coloring media of the aminoalkylsilicon compounds-- to solid and fibrous substrata including, amongothers:

(1) materials of normally good substantivity or afiinity forconventional coloring agents, such as natural fibrous substrata andmonofilaments derived from animal and vegetable fibers, andsemisynthetic fibers from natural raw materials; whereby enhanced use ofat least some of the existing coloring agents for these materials can berealized, as well as wider use of certain other coloring agents whichhave heretofore found only limited acceptance in connection with thecoloring of these substrata; and

(2) normally difiicultly colorable substrate materials, including (A)natural fibrous materials such as leather and asbestos fibers; (B)natural solid substrates including inorganic oxides in pulverulent orlaminate forms such as silica, titania, quartz, mica, diataomaceousearth, siliceous sands and gravels etc., and metallic substratacontaining similar spontaneously-formed insoluble oxide surface layers;(C) semisynthetic fibrous materials including glass fibers and aluminumsilicate fibers; (D)

. synthetic fibrous substrata, monofilaments and continuous yarns fromfibers such as the polyamides, polyacrylonitriles, polyacrylonitrilesmodified with vinyl acetate, copolymers of acrylonitrile and vinylchloride, copolymers of vinyl chloride and vinyl acetate, polymers oftetrafluoroethylene, the polyester fibers, and polyethylene fibers; and(E) mixed or blended fibrous substrata produced by spinning combinationsof selected natural, semisynthetic, and synthetic fibers from among theabove-enumerated fibrous materials; whereby enhanced coloration of suchsubstrata can be effected by relatively simple techniques and throughuse of a great variety of coloring agents which are presently viewed asbeing substantially nonsubstantive or non-affinitative towards thesematerials.

Whereas the processes and compositions of my copending application areoperative for purposes of promoting initial coloration of such substratematerials by pretreatment with, or concurrent use during the coloringcycle, of the aminoalkyl silicones in their capacity as coloringassistants, the after-treatment processes of my present invention may beapplied to promote enhanced preservation or fastness of such dyeings andprintings through use of the aminoalkyl silicones in their capacity asafter-treating dye-fixatives. That is to say, it should be apparent thatone could effect a primary coloring operation with a substantivedyestuif according to the principles of my copending application, andthereafter promote enhanced fixation of the dyestuif to the substratematerial by aftertreatment of the substrate in accordance with theprocessing techniques of my present invention. In a similar manner, theprocesses of the present invention may be employed to promote dye-fixingof coloring agents deposited on the foregoing types of substrata by anymeans, wherein the resulting dyed or printed substrate might exhibitgenerally inferior fastness properties.

As a result of a relatively extensive screening of the known aminoalkylsilicones, it has been demonstrated that virtually all stable members ofthis series, as well as their coordinated metal complexes, can beemployed as dye-fixatives according to the processing techniques of myinvention, although, unexplainably, certain of these compounds andcompositions and their corresponding metallic derivatives do exhibitsomewhat superior fixing properties towards most of the substantivedyestuffs, as compared with certain other members of the series. It isessential, only, that the dye-fixatives contain at least one grouping ofthe formulation:

wherein the divalent R-linkage between the silicon atom and aminonitrogen atom preferably constitutes a linear or cyclic hydrocarbonchain of three (3) or more carbon atoms chain-length, on which the aminonitrogen is substituted no closer than the third carbon atom removedfrom silicon as, for example, a polymethylene chain of three or morecarbon atoms, or a para-substituted cpyridyl radical, and the like. Thedivalent R-linkage may be unsubstituted or carry additional hyrocarbonsubstituents along its length. The free valences of the amino nitrogenmay both be substituted with hydrogen atoms in primary amine fashion, oras imine (secondary) or nitrile (tertiary) structures carrying organicgroups. Illustrative of the organic groups which can satisfy the freevalences of the amino nitrogen are the simple alkyl radicals orsubstituted alkyl groups, particularly those groups which containcarbon, hydrogen and oxygen atoms or carbon hydrogen and nitrogen atomsor carbon hydrogen, nitrogen and oxygen atoms as for example,aminoalkyl, polyaminoalkyl, hydroxyalkyl, alkoxyalkyl, polyalkoxyalkyl,cyanoalkyl, carboakoxyalkyl or carboxyalkyl radicals, and/or arylsubstituents such as phenyl or pyrrolidyl radicals, or fused aromaticring structures such as naphthlene, and the like. Alternatively, thenitrogen atom may be symmetrically substituted in bis-imine ortris-nitrile fashion by means of other polymethylenesilylidyne groupings[-(CH SlE]. The free valences of the one or more silicon atoms may besatisfied with mixed alkoxy and alkyl or aryl substituents wheremonomeric silanes are involved, or with Si-- linkages and aryl and alkylradicals in the case of aminoalkylpolysiloxanes or copolymers ofaminoalkylpolysiloxanes with other polysiloxanes. In essence, therefore,illustrative functional grouping required in the dye-fixatives of theinvention can be represented in general by the following formula:

wherein R is a substituted or unsubstituted hydrocarbon group of atleast 3 carbon atoms chain-length; R and R" represent members selectedfrom the group consisting of hydrogen, alkyl, aminoalkyl, cyanoalkyl,hydroxyalkyl, carboalkoxyalkyl, carboxyalkyl, and aryl radicals, and themonovalent grouping:

X is a member selected from the group consisting of alkoxy andsiloxylidyne radicals [ESiO-]; and Y and Z are members selected from thegroup consisting of alkoxy, alkyl and aryl radicals.

As indicated above, the necessary functional aminoalkyl silicon groupingof the dry-fixatives of my invention may be contained within a monomericaminoalkylalkoxysilane, an aminoalkylpolysiloxane, or a copolymer orsimple blend or mixture of an aminoalkylpolysiloxane with one or moreother siloxanes. It is not essential that these materials be employed inpure form but crude hydrolyzates or aqueous and aqueous-alcoholicsolutions of the silicones can be employed directly to introduce theaminoalkyl silicon groups onto the dyed or printed substrate materials.

Aminoalkylalkoxysilanes which can be employed in practicing my inventioncan be represented in general by the following formula:

wherein R, R and R" have the same meanings as previously assigned above;X is an alkoxy radical; Y is a member selected from the group consistingof alkyl and aryl radicals; b is zero or a whole number of from 1 to 2;and the sum of c-i-b is not greater than 3 and preferably not greaterthan 2.

The following specific silanes are illustrative of some of theaminoalkylsilyl-functional derivatives included (III) among the class ofcompounds defined within Formula 11 above:

beta-methyl-gamma-aminopropyltriethoxysilanegamma-aminopropyltriethoxysilane gamma-aminopropyltripropoxysilanegamma-aminopropylmethyldiethoxysilanegamma-aminopropylethyldiethoxysilanegamma-aminopropylphenyldiethoxysilane delta-aminobutyltriethoxysilanedelta-aminobutylmethyldiethoxysilanedelta-aminobutylphenyldiethoxysilanegamma-aminoisobutylmethyldiethoxysilane gamma-aminobutyltriethoxysilanegamma-aminobutylmethyldiethoxysilaneN-beta-carbethoxyethyl-gamma-aminopropyltriethoxysilaneN-gamma-aminopropyl-delta-aminobutylmethyldiethoxysilaneN-gamma-aminopropyl-gamma-aminopropyltriethoxysilaneN-beta-aminoethyl-gamma-aminopropyltrimethoxysilaneN-beta-cyanoethyl-delta-aminobutyltriethoxysilaneN-gamma-triethoxysilylpropyl-pyrrolidineN-gamma-tricthoxysilylpropyl-Z,S-dimethyl-pyrrolidineN-phenyl-N-methyl-gamma-aminopropyltriethoxysilaneN-phenyl-N-methyl-delta-aminobutyltriethoxysilaneN-methyl-beta-methyl-gamma-aminopropyltriethoxysilanebis(gamma-triethoxysilylpropyl)imine bis(beta-methyltriethoxysilylpropyl) imineN,N-dimethyl-gamma-aminopropyltriethoxysilaneN-naphthyl-N-methyl-gamma-aminopropyltriethoxysilaneN-(furfuryl)-gamma-aminopropyltriethoxysilane, etc.

Aminoalkylalkoxysilanes of the foregoing type and methods for producingcompounds of this structure, in general, are described and claimed inUS. 2,832,754 issued on Apr. 29, 1958. In addition, those silanes whichcontain two amino nitrogen atoms can be prepared by the reaction of adiamine with the appropriate chloroalkylalkoxysilane.

The alkoxysilylalkylamines, -imines, -nitriles are generallycharacterized by their ability to form stable solutions with aqueousadmixtures of organic compounds, which is a particularly desirableproperty from the standpoint of existing practices employed in thetextile finishing industries. When placed in aqueous solution, thealkoxy groups hydrolyze at a slow rate such that the silane monomers areeventually converted to water-soluble aminoalkylpolysiloxanes. Aqueousadmixtures of such polysiloxanes with water-soluble organic compoundsconform to most requirements of stability encountered in the textilecoloring and finishing industries.

The aminoalkylpolysiloxanes which can be employed to carry the desiredfunctional group represented by Formula I above for purposes of myinvention, may be linear, cyclic or cross-linked in nature. Theaminoalkylpolysiloxanes of the cross-linked variety are readily producedby the hydrolysis and condensation of the trialkoxy-substitutedsilylalkylamines, -imines or -nitriles, and can contain small amounts ofsilicon-bonded hydroxyl groups or silicon-bonded alkoxy groups dependingon the conditions under which polymerization is conducted. For example,aminoalkylpolysiloxanes of this type which are essentially free ofresidual silicon-bonded alkoxy or hydroxyl groups can be produced by thecomplete hydrolysis and total condensation of anaminoalkyltrialkoxysilane, whereas polymers containing predominantproportions of residual alkoxy groups can be produced by the partialhydrolysis and total condensation of the same starting silane. In asimilar manner, polymers containing predominant proportions of residualsilicon-bonded hydroxyl groups can be produced by essentially completehydrolysis and only partial condensation of the trifunctional silanestarting materials. Polysiloxanes of the foregoing types may berepresented in general by the following unit structural formula:

wherein R, R and R" have the same meaning as previously assigned above;Z represents hydroxyl and alkoxy groups; and d has an average value offrom to 2, and preferably from 0 to 1. Typical polymers from among thecompounds of this class include, gamma-aminopropylpolysiloxane,delta-aminobutylpolysiloxane, etc., and related hydroxylandalkoxy-containing hydrolyzates and condensates of these polymers.

Aminoalkylpolysiloxanes of the cyclic and linear varieties may beproduced readily by the hydrolysis and condensation of dialkoxyalkylordialkoxyarylsilylalkylamines, -imines, and -nitriles. These polymers maybe represented in general by the following structural formula:

1 IR-E liO lit/I n wherein R, R and R" have the same meanings aspreviously assigned above; Y is an alkyl or aryl radical; and n is aninteger having a value of at least 3, with average values of from 3-7for the cyclic polysiloxanes, and higher for the linear polysiloxanes.Typical cyclic polymers from among this class include the cyclictetramers of gammaaminopropylmethylpolysiloxane anddelta-aminobutylmethylpolysiloxane, and the like. The linear polymersmay be structures of the type of gamma-aminopropylmethylpolysiloxane,gamma aminopropylethylpolysiloxane, delta-aminobutylmethylpolysiloxane,gamma-aminobutylmethylpolysiloxane, and the like. The linearaminoalkylpolysiloxanes further include alkyl, alkoxy and hydroxylend-blocked materials which contain from 1 to 3 such groups bonded tothe terminal silicon atoms of the molecules comprising the polymericchains. For example, linear polymers such as monoethoxy end-blockedgammaaminopropylethylpolysiloxane, methyldiethoxysilyl endblocked deltaaminobutylmethylpolysiloxane, monoethoxydimethylsilyl end-blockedgamma-aminopropylphenylpolysiloxane, and the like, may be employed toimpart the desired functional groups to a dyed or printed substrate.,These end-blocked polymers may be readily produced by the equilibrationof cyclic aminoalkylpolysiloxanes with silicon compounds containingpredominant silicon-bonded alkoxy groups, or by the cohydrolysis andcondensation of trialkylalkoxysilanes withaminoalkylalkyldiethoxysilanes or aminoalkylaryldiethoxysilanes. Thehydroxyl end-blocked polymers can be prepared, also, by heating linearor cyclic aminoalkylpolysiloxanes with water.

The copolymeric polysiloxanes which can be employed as dye-fixatives inaccordance with my invention may contain siloxane units consisting ofany of the typical siloxyalkylamine, -imine or -nitrile groups depictedabove, in combination with one or more other hydrocarbon-substitutedsiloxane units of any desired configuration, as represented in generalby the formula:

(VI) we wherein W and W are hydrocarbon radicals; and e is an integerhaving a value of from O to 2. These copolymers may be produced by thecohydrolysis and condensation of typical aminoalkyl silanes with otherhydrocarbonsubstituted silanes, or by the direct equilibration ofseparate polymeric starting materials. The linear copolymers can alsocontain chain-terminating or end-blocking groups such as alkyl, hydroxyland alkoxy radicals. The Various polymeric and copolymeric materials ofthe types discussed hereinbefore, as well as processes for producingthese materials, have also been described in substantial detail andclaimed in the aforementioned copending applications.

As indicated hereinbefore, the aminoalkyl silicone dyefixatives may alsobe employed in the form of their metal coordinated complexes withmetallic components of the type of copper, chromium, cobalt, etc. Ofprimary interest are the copper complexes of the base resins andmonomeric silanes, which may be prepared by simple aqueous reaction ofthe silicones with water-soluble copper derivatives such as cupricchloride, acetate or sulfate, or waterdispersible or insoluble copperderivatives such as the hydroxide, stearate and the like. It has beenpostulated, heretofore, that copper is capable of forming a bridgebetween the dyestuff molecule and the dye-fixing agent, with a resultingtendency to stabilize the dyestuff towards fading with light. Ingeneral, the aminoalkyl silicone dyefixatives of the invention can besupplied in the form of the base resins for direct use as aftertreatmentagents, or they can be supplied in pre-complexed form, or combined withthe complexing copper derivative at the time of use to form coppercoordinated complexes, in situ, Within the aftertreatment bath.

While all of the aminoalkyl silicones seemingly are operative forpurposes of promoting washfastness of dyestufis on the various substratadescribed, I have found that certain compounds and compositions appearto approach a more universal dye-fixing status from the standpoint ofthe numerous different types of dyestufis and substrata customarilyemployed by the dyeing and finishing industries. The specific compoundsand compositions listed below have been found to be particularlyefficient as dyefixatives of the universal type:

(A) Homopolymer of delta-aminobutylmethylpolysiloxane and coppercoordinated complexes thereof;

(B) N-beta-cyanoethyl-delta-aminobutylmethylpolysiloxane; and

(C) Crude hydrolyzates of delta-aminobutylmethylpolysiloxane.

Still other compounds and compositions of unique performancecharacteristics have been identified within the detailed experimentaldata presented hereinafter.

It is believed that my invention may be best understood by reference tothe following specific examples which illustrate the foregoingprinciples and procedures as applied to the dye-fixing, on Warious typesof substrate material, of different classes of dyestuffs by means of aplurality of typical different aminoalkyl silicones and coordinatedmetal complexes of the aminoalkyl silicones. For the sake of convenienceand brevity, the various noncomplexed aminoalkyl silicones which wereemployed as dye-fixatives within the experimental work reported in theexamples, as consolidated in tabulated form in Table I below, andnumber-coded for ease of reference in the actual text of the examples.

TABLE I Dye fixatives numetal code designation Compound or compositionand and

TABLE IContinued tives nu- Compound or composition meral codedesignalion 9 Homopolymer of delta-aminobutylmethylpolysiloxane.

10 Copolymoric silicone oil comprised of 75% trimethylsiloxy end-blockeddimothylsiloxano and 25% of delta-aminobutylmothylsiloxy groups.

11 Copolymcric silicone oil comprised of gamma-ammopropyltriethoxysilaneand vinyltriethoxysilane (25% resin solids).

12 Copolymeric silicone oil comprised ofgamma-aminopropyltrlethoxysilane and amyltriethoxysilane (30% resinssolids).

13 Cobrg; Sholate of gamma-armnopropyltriethoxysilane (17% 14Copolymeric silicone oil comprised of 83.3% trimethylsiloxy end-blockeddimethylsiloxane and 16.7% gamma-aminopropylsiloxy groups.

15 Gammo-aminopropylpolysiloxane; the homopolymer fromgamma-aminopropyltriethoxysilano (50% solids in ethanol).

16 N-naphthyl-ga1nma-aminopropyltriethoxysilano.

17 Copolymer comprised of 50% trimethylsiloxy end-blockeddimethylsiloxane and 50% dclta-aminobutylmethylsiloxy groups.

18 Copolymer comprised of 70% trimethylsiloxy end-blockeddimethylsiloxane and 30% N,N-bis(beta-hydroxyethyl)-delta-aminobutylmothylsiloxy groups.

19 Copolymer comprised of 27% trimethylsiloxy end-blockeddimethylsiloxane, 40% diphenylsiloxy groups, and 33%delta-aminobutylmethylsiloxy groups.

20 Copolymcr comprised of 68.5% trimethylsiloxy end-blockeddimethylsiloxano, diphenylsiloxy groups, and 6.5%dclta-amiuobutylmcthylsiloxy groups.

21 N-gamma-tricthoxysilypropylpyrrolideno hydrochloride.

. N-bota-cyanoethyl-dclta-aminobutyltriethoxysilane.

23 NaNddimothyl-garnma-aminopropyltriethoxysilane hydrolo- 24Beta-methyl-gamme aminopropyltrlethoxysilane.

25 Bis-(beta-methyltrietho xysilylpropyDimine.

26 N-methyl-beta-mcthyl-gamma-ami nopropyltriethoxysilane.

27.-. N-beta-carbcthoxyethy1gamma-aminopropyltriethoxysilano.

28.-- N-beta-cyanoethyl-dclta-aminobutyhnethylpolysiloxane (mainlycyolics) 20. N-(beta-Iuriuryl)-gamma-aminopropyltriethoxysilane.

30- Delta-aminobutylmcthyldiethoxysilano.

31.. Dolta-ominobutylmothylpolysiloxano (crude product otherwisecomparable to 9 above; made by non-solvent hydrolysis of 30).

32 Same as 31 except made by solvent hydrolysis.

33 Delta-aminobutyhncthylpolysiloxane incompletely condensed and thusprobably containing silicon-bonded ethoxy or hydroxyl groups (60% solidsin ethanol).

34 Aminomethyltriethoxysilanc.

35. N-l eta-aminoethyl-gannna-aminopropyltriethoxysrlane.

36 Copolymer comprised of 60% trimethylsiloxy end-blockeddimethylsiloxane and 40% N-betaaminoethyl-gammaaminoisobutylmethylsiloxygroups.

37 N, III-bis(beta-hydroxypropyl)-garnma-aminopropylpolys1 oxane.

38 N,N-bis(beta-hydroxystearyl)-gamma-aminoisobutylmethyldiethoxysilane.

39 N-oetyl-gamma-aminoisoloutylmothyldiethoxysilane.

EXAMPLE I Cotton Substrate: Direct Dyestuif Swatches of white,kier-boiled and bleached cotton sheeting were dyed with a dye having aColor Index number of 29225, a direct dyestufii, in a dye bathconsisting of 1% of the dyestuff and a volumezfa bric ratio of 40:1, at180 F. The swatches were dyed for 20 minutes after which time 15% sodiumchloride on fabric weight was added to increase exhaustion. The dyeingwas then continued for 15-20 minutes more, and the dyed swatches werethereafter removed from the dye bath and rinsed with water.

The dyed cotton swatches were individually placed in 1% solids solutionsof aminoalkyl silicone dye-fixatives Nos. 1, 4, 8, 9 and 10 (Table I),containing 1% acetic acid and a 50/50 mixture of water and isopropanol,at room temperature. After stirring in these solutions for 15 minutes,the swatches were removed, rinsed in cold water and dried for fiveminutes at 250 F. After drying, a white piece of cotton was stapled ontoeach of the dyed and silicone-treated swatches. These specimens werethen individually immersed in water (160 F.), stirred for one hour,removed, rinsed, and finally dried. The color removal on the cloth, thecolor of the wash liquor, and the degree of transfer of color to thewhite swatch were noted for each of the treated swatches and closelycompared to a dyed swatch which was not aftertreated with a dye-fixingagent. In all cases, the aminoalkyl silicone dye-fixatives hadappreciably improved the fastness of the dyestuif as determined by allthree test properties. The respective dye-fixatives were rated in orderof increasing improvement in washfastness as follows:

Untreated Control-Poorest Dye-Fixative No. 1 Dye-Fixative No. 4Dye-Fixative No. 9 Dye-Fixativc No. 10 Dye-Fixative No. 8Best EXAMPLE IIViscose 'Rayon Substrate: Direct Dyestuffs Five (5) viscose rayonfabrics which had previously been dyed in a mill with a red, aturquoise, a navy blue, a brown and a copper brown direct dyes, wereeach finished with aminoalkyl silicone dye-fixatives Nos. 1, 3, 4, 8, 9,10, 11 and 12 to improve the washfastness of the dyes. In thesefinishings, a 5% solution of each dye-fixative was made in a 50water-isopropanol mixture containing 5% acetic acid. The swatches ofdyed viscose were padded with each dye-fixing solution at 65% wetpick-up, and then dried for 5 minutes at 320 F.

After the drying operation, the washfastness of the dyes was determinedin accordance with the same test procedures described in Example I. Aswatch of each dyed fabric that had not been with a dye-fixative wasalso tested for comaprison. Again, on all five dyed fabrics, all of thedye-fixatives tested improved the washfastness of the dyestulf in thefollowing approximate orders of effectiveness, from poorest to best. Thenumerical designations of the various dye-fixatives correspond to theirlisting in Table I.

Rayon Substrate: Direct Dyestuifs (A) Dye-fixatives Nos. 1, 8, 9 and 10,and a leading commercial dye-fixing agent consisting of a coppercoordinated metal complex of an amine resin, were each applied to a navyblue and a brown direct-dyed rayon fabric at various concentrations. Inthis series of tests, the commercial dye-fixative was dissolved inwater. The aminoalkyl silicone dye-fixatives were dissolved in a 50/ 50mixture of isopropanol and water containing 1% by weight of acetic acid.Swatches of the dyed fabrics were padded through the solutions at wetpickup and dried for 10 minutes at 300 F. The concentrations ofdye-fixatives employed were as follows:

Solution concentration: Deposited on cloth, percent The treated swatchesof fabrics were stapled to a white piece of cotton and were individuallyimmersed in beakers of water at 160 F. They were then held, withperiodic stirring, at 160 F. for one hour, removed, rinsed and finallypressed dried. The color of each water extract was again noted, as wasthe transfer of color to the white cotton bleeder.

At these reduced concentrations, aminoalkyl silicone dye-fixative No. 9,at all concentration levels and on both dyed fabrics, producedsubstantially better dye-fixing effects than the commercialdye-fixative. The commercial dye-fixative produced the next bestresults, and was closely followed by dye-fixatives Nos. 10, 8 and 1, inthat order of etficiency.

(B) A further type of dye-fixing application was performed involving useof dye-fixative No. 9 in a typical resin finishing bath containingconventional wrinkle-proofing and stabilizing resins. Two differenttypes of resin finishing mixes were employed, and a direct-dyed navyblue rayon fabric was used for the tests. The following compositionswere evaluated:

10% urea-formaldehyde resin (50%) 1% 2-amino-2-rnethyl-l-propanolhydrochloride (30% solution) (catalyst) 1% dye-fixative No. 9

10% urea-formaldehyde resin (50%) 1% 2-amino-2-methyl-l-propanolhydrochloride (30% solution) (catalyst) 1% commercial dye-fixative(copper complex of amine resin) 10% urea-formaldehyde resin (50%) 1%2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst) Nodye-fixing agent 30% urea-formaldehyde paste resin (60%) 1.5%2-amino-2-methyl1-propanol hydrochloride (30% solution) (catalyst) 1%dye-fixative No. 9

30% urea-formaldehyde paste resin (60%) 1.5 2-amino-2-methyl-l-propanolhydrochloride (30% solution) (catalyst) 1% commercial dye-fixative(copper complex of amine resin) 30% urea-formaldehyde paste resin (60%)1.5% 2-amino-2-methyl-l-propanol hydrochloride (30% solution) (catalyst)No dye-fixing agent Untreated dyed fabric In preparing the foregoingsolutions, dye-fixative No. 9 was employed in solution form containing10 parts of the aminoalkyl silicone, 1 part acetic acid and 89 parts ofa 50/50 water-isopropanol mixture. The rayon fabric swatches were paddedat 60% wet pick-up and cured for 5 minutes at 320 C. The dye-fixingproperties were then evaluated by the procedures described in thepreceding examples.

It was found that the finishing resins alone produced only a very slightdye-fixing efifect. Aminoalkyl silicone dye-fixative No. 9 and thecommercial dye-fixative produced approximately equal dye-fixing, but No.9 was better than the commercial agent in resin mixes l and 2 above,whereas with resin mixes 4 and 5, the commercial dye-fixative wasslightly superior.

These tests demonstrate that the aminoalkyl silicone dye-fixatives arecompatible with standard thermosetting 14 finishes such that they may beapplied both in the dyeing operation and in the finishing stages.

EXAMPLE IV Rayon Substrate: Direct Dyestuff with Copper CoordinatedComplexes Several copper coordinated complexes of aminoalkyl siliconedye-fixative No. 9 were prepared on the basis of the followingformulations:

Complex Complex Complex Components 9-A 9-B 9 C Moles of dye fixative No.9 l. 0 1. 0 0. 5 Moles of Ouch-21110 1.0 0. 5 1. n

respective pH values:

pH with Complex pH alone acetic acid With no acid, all three complexesgave cloudy solutions, whereas with the acid, all solutions were clearand blue.

All six of the complex solutions were padded onto the dyed fabrics at60% wet pick-up so as to deposit 0.6% solids of the complex. Theswatches of cloth were then dried for 10 minutes at 300 F. The dyefixing properties were evaluated by the procedures described in thepreceding examples. In all cases superb dye-fixation was obtained. Thethree acid solutions appeared to show equal performance for all three ofthe copper-silicone complexes. In the non-acidified samples, complex 9Ashowed slightly inferior fixing action, but this complex also gave themost cloudy solution ad coarse dispersion.

EXAMPLE V Rayon Substrate: Direct Dyestuff with Cobalt ChelateDye-fixative No. 13, consisting of a cobalt chelate ofgamrna-aminopropyltriethoxysilane (17% in H O), was applied to a brownand navy blue direct-dyed rayon substrate at 1% pad solids concentrationand 60% wet pickup, followed by drying for 10 minutes at 300 F. andtesting by the usual procedures. On the brown fabric, this dye-fixativegave excellent dye-fixation, whereas on the navy-dyed fabric, thedye-fixing properties were somewhat less eflicient.

EXAMPLE VI Viscose Rayon Challis: Direct Dyestuffs In an effort tofurther evaluate the dye-fixing properties of dye-fixative No. 9 ascompared with those of a leading commercial amine resin dye-fixative, adirect dyestuff having a Color Index number of 29225 was selected forlaboratory dyeings on viscose rayon challis. In the actual dyeings, thedye bath contained 2% dye on the weight of the cloth samples. Thefabriczbath ratio was 30.1. The dyestuff was pasted with small amountsof a sodium alkyl sulfate wetting agent and water to full volume. Thesamples of fabrics were wet and then placed in the dye bath. The bathtemperature was then raised to 180 F. gradually. After 15 minutes ofdyeing, 7.5% of Glaubers Salt on fabric weight was added to the dyebath. Dyeing was continued for 15 more minutes, 7.5 additional GlaubersSalt was added, followed by 15 minutes more dyeing at 180 F. The sampleswere then removed from the dye bath, rinsed in cold water and dried.

The following treatments were applied to each of the above dyed fabricsfor dyefixing tests:

(A) Control-none;

(B) 0.5% of dye-fixative No. 9, plus 1% acetic acid in water;

(C) 0.5% of commercial dye-fixative in water.

The samples were padded at 60% wet pick-up to deposit 0.3% dye-fixingagent based on the weight of the cloth. They were then dried and curedfor 10 minutes at 300 F.

Dye bleeding and staining tests were made as previously described andrated on the basis of the following schedule:

Rating of 4=heavy dye bleeding and staining Rating of 3=medium dyebleeding and staining Rating of 2=light dye bleeding and staining Ratingof 1=minor dye bleeding and staining Rating of =no bleeding and nostaining The results of these dye-fixing studies are presented intabulated form in Table II below, based on the foregoing rating scale.These results establish that with the particular dyestuff used,dye-fixative No. 9 is superior to the commercial dye-fixative inpreventing bleeding of the dye in water at 160 F., and in preventingstaining of white fabrics.

TABLE II [Comparison of aminoalkyl silicone dye fixative No. 9 andcommercial agent in dye fixing of direct dyed rayon substrata] Dyebleeding and staining ratings Viscose Gabardine: Direct dyestuifs withchromium coordinated complexes A series of chrome metal coordinatedcomplexes were prepared using arninoalkyl silicone dye-fixatives Nos. 9and 10. These modified dye-fixatives were prepared as water solutions orpastes containing 20% solids complexes based on the followingformulations:

Complex designation: Composition 9-A 1 mole CrCl to 1 mole dye-fixativeNo. 9

9-B' 1 mole CrCl to 2 moles dye-fixative No. 9

9-C' 1 mole CrCl to 3 moles dye-fixative No. 9

10-A 1 mole CrCl to 1-NH EQ. in dye-fixative 10-B 1 mole CrCl to 2-NHEQ. in dye-fixative l0-C 1 mole CrCl to 3-NH EQ. in dye-fixative Withdye-fixative No. 9, the chromic chloride was dissolved separately inwater, and then the aminoalkyl silicone was added with stirring. Heatwas evolved. The solutions were cooled with stirring and bottled. Thecomplexed dye-fixatives Nos. 9-A', 9-B', and 9-0 were dark opaque greenliquids. On dilution with water, all samples gave cloudy dispersions. Onadding acetic acid, all formed clear dark green solutions.

In the case of the dye-fixative No. 10 complexes, the chromic chloridewas also dissolved separately in water, and the aminoalkyl silicone wasdissolved in isopropanol and then added to the salt solution. In allcases, heat was evolved on mixing. Complexed dye-fixative No. 10-A was adark green solution, whereas Nos. 10-B and 10-0 16 were dark greendispersions. All formed cloudy dispersions on dilution with water whichcleared by the addition of acetic acid.

The foregoing metal complexes were comparatively tested on a scarletdirect-dyed viscose gabardine cloth which is normally finished with acommercial amine resin type of dye-fixative. The latter agent was alsotested along with an untreated control. Comparisons were made at 0.5%solids concentration in padding solution. As an additional control, asample was also treated with dyefixative No. 9 alone.

The treatments were conducted as described in the preceding examplesfrom aqueous solutions containing 1% acetic acid, followed by drying andcuring at 300 F. for 10 minutes. The bleeding tests were run at F.

The results of these tests are presented in tabulated form in Table IIIbelow, based on the dye-fixing scale of Example VI. These data show thatthe 0.5% chrome complexes of dye-fixative No. 9 in the padding bath gaveabout the same results as 0.5 of No. 9 alone and 0.5% of the commercialdye-fixative. At the 0.5 concentration, the chrome complexes ofdye-fixative No. 10 were not as effective. Significantly, however,whereas the commercial fixative changed the initial shade of thisdyestuif from scarlet red to a deep blue maroon color, all of the othersamples retained the original dye shade.

TABLE III Comparative dye-fixing with chrome complexes of dyefixativesNos. 9 and 10, dye-fixative No. 9 alone and commercial amine resindye-fixative Scale of bleeding and staining Lw-hOOOOO-P EXAMPLE VIIIRayon Substrata: Direct dyestuffs under severe washing conditions andlightfastness tests (A) The degree of washfastness of direct-dyedfabrics after-treated with dye-fixing agents is evaluated by a largenumber of procedures depending upon the particular performancecharacteristics required for the finished products. For example, somefabrics need only possess resistance to cold water bleeding, whereasothers must have resistance to hot wateror hot soap washes. In general,the best overall fastness is obtained on rayons when the dyefixingagents are combined with thermosetting resins. Furthermore, theconcentrations of dye-fixatives used by a textile plant generally riseas the degree of fastness is increased. Since the aminoalkyl siliconedye-fixative No. 9 and its metal coordinated complexes are extremelyeflicient at relatively low concentrations for both cold and hot waterbleeding, testswere conducted to evaluate these products from thestandpoint of required concentrations under more drastic washingconditions.

In a first series of tests, three direct-dyed rayon fabrics were treatedwith the following formulations from aqueous solutions:

1% dye-fixative No. 9+1% acetic acid 1% diye-fixative No. 9-C (coppercomplex)+1% acetic act 1% dye-fixative No. 9-B' (chrome complex)+1%acetic acid 1% dye-fixative No. 17+1% acetic acid 1% commercial amineresin dye-fixative Untreated control 17 The treatments were conducted asdescribed in the preceding examples. After curing, the samples weretested by a modified AATCC No. 2 wash test using 0.5% of a commercialsoap flake product at 120 C. for 30 minutes followed by two rinses at105 F. and flat bed pressing.

A second series of dye-fixatives was prepared using 3% solids of thevarious dye-fixing formulations listed above. These samples were testedin soap solution by a different test procedure at 140 F.

A third series of samples of the 3% paddings was given the No. 3 AATCCwash test using 0.5% soap and 0.5 sodium carbonate for 45 minutes at 160F. The results of these tests are all presented in tabulated form inTable IV below on the basis of the rating scale of Example VI.

In the evaluation of these results it was very difiicult to give ratingscomparable with the commercial dye-fixative because of the verydifierent shades produced. Moreover, bleeding evaluations could not beemployed as such since in these soap solutions, the white cotton testpiece was initially colored, but the color was then removed by the soapwash. Evaluation ratings were arrived at by examining the amount ofcolor removed and by the stain left on the White cotton bleeders. As anoverall result of these testings, it can be concluded that dye-fixativesNos. 9 and 17 yield performance characteristics similar to or betterthan the commercial dye-fixative.

TABLE IV [Comparative dye-fixing efficiencies of selected aminoalkylsilicone dyefixatives and commercial product under severe washingconditions] Loss of color on washing (B) In an effort to evaluate theeffects of the aminoalkyl silicone dye-fixatives on lightfastnessproperties, the samples of the brown fabric treated with the 1% productsin the preceding section were subjected to Fadeometer exposures andexamined for fading every 20 hours. The results of these tests arepresented in tabulated form in Table V below. With reference to thesedata, it will be seen that dye-fixatives Nos. 9 and 17 without metalsreduced the lightfastness of this particular dyestuff. On the otherhand, both the copper and chromium complexes greatly improved resistanceto fading. The copper complex of dye-fixative No.9 (9-A) was equivalentto the commercial dye-fixative.

TABLE V [Fadeometer studies on direct dyestufl aftertreated with variousdyefixing agents] Fading rating* 40 hours 60 hours 80 hours Dye-fixativeemployed 20 hours *N N B =No appreciable break-good; SB =Slightbreak-good; AB Appreciable break-fair.

18 EXAMPLE IX Rayon Substrate: Direct dyestuff with various aminoalkylsilicone dye-fixatives (A) A group of different aminoalkyl siliconedye-fixatives were compared on a single brown rayon direct-dyed fabricusing 1% solids in the padding bath at 60% Wet pick-up followed by theusual drying and curing and hot water bleeding tests. The results ofthese studies are presented in tabulated form in Table VI below based onthe rating scale of Example VI. On the basis of 0.6% deposited solids,it was found that dye-fixatives Nos. 18, 19 and 23 (Table I) were themost efficient. Significantly, these covered primary, secondary andtertiary amino groups within the aminoalkyl silicones. The aromaticphenyl and naphthyl amine based silanes (dye-fixatives Nos. 7 and 16,respectively) were relatively ineffective at this concentration.

TABLE VI Dye-fixing efficiency of miscellaneous aminoalkyl siliconedye-fixatives and controls Dye-Fixative: Dye bleeding and staining (B)Additional dye-fixing tests were conducted with dye-fixatives Nos. 9, l0and 17 at 0.5% pad bath solids concentrations using aqueous solutionscontaining 1% acetic acid. The padding procedures and tests wereconducted as described in the preceding examples. Four different directdyestuffs were used.

The results of these tests are summarized in tabulated form in Table VIIbelow on the basis of the rating scale of Example VI. The data show thatdye-fixative No. 10 is the least effective agent at this concentration,whereas both dye-fixatives Nos. 9 and 17 are superior to the commercialamine resin dye fixative. On the scarlet fabric, for example, while noneof the aminoalkyl silicone dye-fixatives produced any change in shade,the commercial dyefixative produced a blue maroon color.

TABLE VII [Dye-fixing efficiency of aminoalkyl silicone dyefixativesNos. 9, 10 and 17 on direct-dyed rayon fabric at 0.3% deposited solidsconcentration] (C) Further dye-fixing tests were conducted withdyefixatives Nos. 5, 9, 14 and 15 in which 1% of each product wasapplied from 1% acetic acid solutions in 5050 water-isopropanol solvent.The results of these studies are 19 presented in tabulated form in TableVIII below on the basis of the rating scale of Example VI.

These results demonstrate the difference in efiiciency between a commonmonomer and polymer (dye-fixatives Nos. 5 and 15, respectively); thelatter showing greatly increased dye-fixing performance. Again,dye-fixative No. 9 gave the best overall performance, however.

TABLE VIII D e-fixin eflicieney i aminoalkyl silicone dye-fixatives Nos.9 1i and lfi on direct-dyed rayon fabrlc at 0.6% deposited sohds'concentration] Dye bleed- Dye-fixative ing and employed Dyestufistaining None Brown 4 No. 5 .d 3 No. 14. 2 No. 15. 1 No. 0 .do 0

None Turquoise 4 N o. 6 .d 3 1 EXAMPLE X Rayon Fabrics: Direct dyestutffixed with crude hydrolyzates of aminoalkyl silicones A series of crudehydrolyzates of aminoalkyl silicones were tested for dye-fixingefliciency in the form of the free resins and as copper coordinatedcomplexes. In these tests, the following two groups of treatingsolutions were prepared in water (all as percentage solids):

GROUP I (1 0.5 dye-fixative No. 9+ 1 acetic acid (2) 0.5% dye-fixativeNo. 31+1% acetic acid (3) 0.5 dye-fixative No. 32+ 1 acetic acid (4) 0.5dye-fixative No. 33,+1% acetic acid (5) 0.5 dye-fixative No. 30+ 1acetive acid (6) 0.5% dye-fixative No. 2+1% acetic acid (7) 0.5%commercial amine resin dye-fixative GROUP II The foregoingaftertreatment solutions were applied to direct-dyed rayon fabric bypadding at 60% wet pick-up, and the fabrics were dried for minutes of300 F. All of the solutions were permitted to age 30 minutes beforeapplication to the cloth swatches.

Those fabrics which had been treated with the low concentrations of theplain aminoalkyl silicone dye-'fixatives (Group I above, 1-7) weretested for bleeding and washfastness by immersion for one hour in waterat 160 F. containing 0.1% of a sodium alkyl sulfate wetting agent, withperiodic stirring. As in the preceding examples, a

20 piece of white cotton fabric was stapled to each dyed sample todetermine dye transfer.

Those fabrics which had been treated with the corresponding coppercoordinated complexes (Group II above, 5 8-14) were tested forwashfastness using a modification of AATCC No. 2 test wherein the dyedsamples and a white cotton control are placed in water at 140 F.containing 0.5% of a commercial soap flake product and agitated for 30minutes.

After each of the above tests, all of the samples were allowed to airdry and then the color loss and transfer to the white fabric were ratedon the basis of the rating scale defined in Example VI.

The results of the Group I series of tests (samples l-7) are shown intabulated form in Table 'IX below. Here at the low concentration andneutral bleeding hot water test, the three crude hydrolyzate-typedye-fixatives were found to be identical in performance to the pureaminoalkyl silicone dye-fixative No. 9, and as good or better than thecommercial amine resin dye-fixative. The two monomeric dye-fixativeswere somewhat inferior to the polymers and showed varying performance onthe four different directdyed fabrics.

The results of the soap wash tests with the Group II series (samples8-14) have been presented in tabulated form in Table X below. Theseresults show that for higher concentrations of dye-fixatives plus copperchloride, there was very little difference between dye-fixative No. 9and the three crude hydrolyzates which performed as well or better thanthe commercial amine resin dyefixative. Here again, the two monomerswere inferior to the polymers. As with previous studies, all of thecopper containing dye-fixatives produced appreciable shade changes ascompared with the pure aminoalkyl silicone products.

TABLE IX Dye fixing efficiency of crude hydrolyzate-type aminoalk lsilicone d fixatives and others on direct-dyed rayon fabric (Groiip 1)]ye Dye-fixative Degree of bleeding and staining 4O employed (Samples1-7) Turquoise Red Copper Brown TABLE X [Dye fixing etliclency of crudehydrolyzate-type, copper-containing Rayon Fabrics: Direct Dyestuifs andMiscellaneous Aminoalkyl Silicone Dye-Fixatives Dye-fixatives Nos. 24,25, 26, 28, 29, 30 and 34 (Table I) were tested for dye-fixingefiiciency on four direct-dyed rayon fabrics at 1% solutionconcentration (percent on solids) with 1% acetic acid. In each case, thesolutions were padded on the dyed fabrics, and then dried for 10 minutesat 300 F. The 160 F.-one hour hot water bleeding test was employed toevaluate dyefixing efficiency. The results of these studies are setforth in tabulated form in Table XI below on the basis of the ratingscale of Example VI. While the samples were difiicult to rate visuallybecause of shade changes during By exhaustion the bleeding tests, all ofthe dye-fixatives tested did perform with various degrees of dye-fixingefficiency. The most efficient compound was No. 28, whereas, as was tobe expected, the aminomethyl compound (No. 34) was most inefiicient.

TABLE XI [Dye fixing efficiency of various aminoalkyl silicone dyefixatives on direct dyed rayon fabric] Degree of bleeding and stainingDye-fixative employed Turquoise Red Copper Brown EXAMPLE XII Cotton andRayon Fabrics: Difiiculty Fixable Direct Dyestuffs A series of fivedirect dyestulfs which are known to be difficult to fix were applied tocotton and rayon fabrics and then aftertreated under various conditionswith dyefixative No. 9. The dyestuffs involved and the concentration ofeach are listed below:

2% direct dye having a Color Index number of 24895 3% direct dye havinga Color Index number of 28160 2% direct dye having a Color Index numberof 29225 3% direct dye having a Color Index number of 22590 2% directdye having a Color Index number of 741 80 In order to obtain varied dataon the performance of the dye-fixative with these dyes, it was appliedover a wide range of conditions using a number of different finishingformulations and methods of application. Thus, the dye-fixative wasemployed in combination with thermosetting finishes :both alone and asthe corresponding metal coordinated complexes. It was also applied inreduced concentrations with non-resin mixes to obtain such effects ascold water fastness, hot water fastness, fastness to perspiration, andfastness to wet and dry pressing. The series of treatments listed belowwere made in each case with all five dyed fabrics:

RAYONS Treatment A Treatment B 1.5% dye-fixative No. 9 1.0% CuCl -2H O1.0% acetic acid Pad at 80% wet pick-up. Dried and cured 10 min./ 300 F.

Treatment C 1.0% dye-fixative No. 9 1.0% acetic acid Pad at 80% wetpick-up. Dried and cured 10 min/300 F.

Treatment D on fabric weight Treatment B By exhaustion 1.5% dye-fixativeNo. 9 1.0% CuCl -2-H O u} on fabric weight 1.0% acetic acid Fabric: Bathratio of 1:10 R.T. to 140 F. in 30 min. Extracted Dried 5 min/250 F.

Treatment F Untreated-Control COTTON Treatment G 20.0% urea-formaldehyderesin (60% 1:1.33 U:F) 1.5% dye-fixative No. 9 1.0% CuCl -2H O 1.0%acetic acid Pad at wet pick-up. Dried and cured 1 0 min/300 F.

Treatment H 10.0% dimethylol ethylene urea 1.5 dye-fixative No. 9 1.0%CrCl -6H O 1.0% acetic acid Pad at 80% wet pick-up. Dried and cured 10min./ 300 F.

Treatment I 10.0% methylated methylol melamine resin 3.2% MgCl -6H Ocatalyst (60% solution) 1.5% dye-fixative N0. 9 1.0% acetic acid Pad at80% wet pick-up.

Dried and cured 10 min/300 F.

Treatment I By exhaustion ZZZ $252232;ijjjjjjjjjj} on fabric WeightFabric: Bath ratio of 1:10 R.T. to F. in 30 min. Extracted Dried 5min/250 F.

Treatment K By exhaustion d 1;: g iff ?i on a r welght Fabric: Bathratio of 1:10 R.T. to 140 F. in 30 mins. Extracted Dried 5 mins./250 F.

Treatment L Untreated-Control All of the 60 samples resulting from theforegoing treatments were tested in the F. hot water bleeding test andthe modified AATCC No. 2 test wherein the dyed samples and a whitecotton control are placed in water at 140 F. containing 0.5% of acommercial soap flakes product and agitated for 30 minutes. The resultsof these tests have been presented in tabulated form in Tables XII,XIII, XIV, and XV, below based on the rating scale of Example VI.

For the cotton samples in the hot water bleeding test (Table XII) alltreatments were equally effective for all of the dyestuffs. Similarresults were found with the rayon fabrics (Table XIV), except for thedirect dye having a Color Index Number of 28160 with three of thetreatments and the directdye having a Color Index number of 22590 withtwo of the treatments.

TABLE XII [Ratings after the 160 F. hot water bleeding tests (cotto11)]Degree of bleeding and staining No. No. No. No. No.

Treatment applied None G H I J K TABLE XIII [Ratings after the modifiedNo. 2 soap wash tests (eotton)] Degree of bleeding and staining No. No.No. No. No. Treatment applied None G H J K Dye on cloth (abbreviated):

TABLE XIV [Ratings after the 160 F. hot water bleeding tests (rayon)]Degree of bleeding and staining [Ratings after the modified No. 2 soapwash tests (rayon)] Degree of bleeding and staining No. No. No. No. No.

Treatment applied None A B C D E Dye on cloth (abbreviated):

EXAMPLE XHI Cotton and Rayon Fabrics: Direct Dyestuffs The followingfour direct dyestuffs were used to dye cotton and rayon fabrics foraftertreatment with aminoalkyl dye-fixative No. 4:

Direct dye having a Color Index of 30145 Direct dye having a Color Indexof 29225 Direct dye having a Color Index of 29065 Direct dye having aColor Index of 29125 The nine rayon samples were cut into swatches andtreated with the following treatment solutions:

Treatment A 30% urea-formaldehyde resin (60% 121.33 UzF) 1.5%dye-fixative No. 9

1.0% acetic acid 1.0% CuCl -2H O Treatment B 30% urea-formaldehyde pasteresin (60% 111.33 UzF) 1.0% acetic acid 1.0% 2-amino-2-methyl-l-propanolhydrochloride (30% solution) (catalyst) Treatment C 30%urea-formaldehyde paste resin (60% 1:1.33 UzF) 2.0% commercial amineresin dye fixative 1.0% 2amino-2-methyl-l-propanol hydrochloride (30%solution) (catalyst) Treatment D None-Control The foregoing treatmentswere elfected by padding at 94% wet pick-up followed by drying andcuring in one operation for 10 minutes at 300 F. The samples were notafterwashed.

The four cotton samples were cut into swatches and treated with thefollowing treatment solutions:

Treatment E 1.5% dye-fixative No. 9 1.0% CuCI -ZI-I O 1.0% acetic acidTreatment F 2.0% dye-fixative No. 9 2.0% acetic acid Treatment G 2.0%commercial amine resin dye-fixative Treatment H None-Control Theforegoing treatments were effected by padding at 70% wet pick-upfollowed by drying for 10 minutes at 300 F. The samples were notafterwashed.

The samples were subject to dye bleeding and washfastness tests asdescribed in the preceding examples. The results of these tests arepresented in tabulated form in Tables XVI and XVII below on the basis ofthe color scale of Example VI.

With reference to the tables, it will be seen that on both the cottonand rayon fabrics, dye-fixative No. 9 produced dye-fixation comparableto that of the commercial dye-fixative. In addition, dye-fixative No. 9plus CuCl was slightly more effective than higher concentrations withoutthe cupric chloride.

TABLE XVI [Dye bleeding and staining of direct-dyed rayon in modifiedNo. 2 soap wash test] Dye bleeding and staining (A) A series oflightfastness studies was conducted on four direct-dyed rayon fabricspreviously used for dyefixing tests. These fabrics were treated with thefollowing difierent agents:

(11) 0.5% dye-fixative No. 9+1% acetic acid (12) 1% commercial amineresin dye-fixative 13) Untreated controls These treatments were effectedby padding followed by drying only for five minutes at 250 F. and noafterrinsing. The results of the Fadeometer tests are tabulated in TableXVIII below. By reference to the table, it will be seen that both thecommercial dye-fixative and the silicone treatments reduced thelightfastness of all four dyestuffs about equal amounts. Furtherexposure, however, did not result in further fading.

TABLE XVIII [Lightfastness tests on direct-dyed rayon fabrics treatedwith aminoalkyl silicone complex and commercial agent] Fadeometerexp0surehours to fade Treatment applied Red Turquoise Copper BrownNone-control 40 40 80 80 Dye fixative No. 9/CuCIz 20 20 40 60 Commercial20 20 40 60+ (B) A further series of lightfastness tests was made on thesame brown direct-dyed fabric used above, and treated with the followingdifferent agents:

fixing agents] Fadeometer exposure hours to fade,

Treatment applied copper brown Noneeontrol 80 Dye fixative N o. 9 40 Dyefixative No. 9/CuOl2- 60 Dye fixative No. 9/Cr0l; 6O

Dye fixative N o. 17 40+ Commercial 60 EXAMPLE XVI When dye-fixatives ofthe type of Nos. 35, 36, 37, 38 and 39 are applied to direct-dyedfabrics in the manner described in Example II good washfastness andresistance to bleeding properties are noted.

Having thus described the subject matter of my invention, what it isdesired to secure by Letters Patent is:

What is claimed is:

1. In a process for improving the fastness of dyeings and prints onpreviously dyed and printed substrata such substrata having been dyedand printed with water-soluble direct dyestuffs, the improvement thatcomprises aftertreating the substrata to deposit thereon a coaing of adye-fixative selected from the group consisting of aminoalkyl siliconesand metal coordinated complexes of the same selected from the groupconsisting of monomeric aminoalkylsilanes, aminoalkylpolysiloxanescopolymers of aminoalkylpolysiloxanes with at least one otherpolysiloxane, blends of aminoalkylpolysiloxanes with at least one otherpolysiloxane and metal coordinated complexes of such aminoalkylsilicones, such aminoalkyl silicone coloring assistant containing oneamino substituent wherein the nitrogen atom of the amino group isconnected to a silicon atom of the silicone directly through a divalenthydrocarbon radical and the amino nitrogen is separated by at leastthree carbon atoms from the silicon atom.

2. Process for improving the fastness of dyeings and prints onpreviously dyed and printed substrata such substrata having been dyedand printed with water-soluble direct dyestufis that comprisesaftertreating the substrate to effect deposition thereon of anaminoalkyl silicone dyefixative selected from the group consisting ofmonomeric aminoalkylsilanes, aminoalkylpolysiloxanes, copolymers ofaminoalkylpolysiloxanes with at least one other polysiloxane, blends ofaminoalkylpolysiloxanes with at least one other polysiloxane, and metalcoordinated complexes of such aminoalkyl silicones, containing at leastone functional grouping of the formula:

wherein R is a divalent hydrocarbon linkage of at least three carbonatoms chain-length, in which the amino nitrogen is substituted at leastthree carbon atoms remove from silicon, R and R represent membersselected from the group consisting of hydrogen atoms, alkyl, cyanoalkyl,hydroxyalkyl, carboxyalkyl, carboalkoxyalkyl and aryl radicals, and themonovalent grouping:

X is a member selected from the group consisting of alkoxy and Si-Olinked siloxylidyne radicals [-O-SiE];

and Y and Z are members selected from the group consisting of alkoxy,alkyl and aryl radicals; and thereafter subjecting the substrate to aheat treatment at an elevated temperature to effect drying and curing ofthe dye-fixative thereon.

3. The process as claimed in claim 2 wherein the aminoalkyl siliconedye-fixative is a monomeric silane selected from the group representedby the formula:

wherein R, R and R have the same meanings as defined within claim 2; Xis an alkoxy radical; Y is a member selected from the group consistingof alkyl and aryl radicals; b has a value of from 0 to 2; c is a wholenumber (if value from 1 to 2; and the sum of c-l-b is not greater t an3.

4. The process as claimed in claim 2 wherein the amino alkyl siliconedye-fixative is a crude hydrolyzate of a monomeric silane selected fromthe group represented by the formula:

wherein R, R and R" have the same meanings as defined within claim 2; Xis an alkoxy radical; Y is a member selected from the group consistingof alkyl and aryl radicals; c is a whole number from 1 to 2; b has avalue of from 0 to 2; and the sum of c+b is not greater than 3. 5. Theprocess as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is an aminoalkylpolysiloxane selected from the grouprepresented by the unit formula:

wherein R, R and R" have the same meanings as defined within claim 2; Zis a member selected from the group consisting of hydroxyl and alkoxyradicals; and d has an average value of from to 2.

6. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is an aminoalkylpolysiloxane selected from the grouprepresented by the formula:

R Yr, I-R-SiO [1 1.

wherein R, R and R have the same meanings as defined within claim 2; Yis a member selected from the group consisting of alkyl and arylradicals; and b is an integer having a value from 0 to 2; and at leastone other siloxane unit represented by the formula:

wherein W and W are hydrocarbon radicals; and e is an integer having avalue of from 0 to 2.

8. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is a mixture of polysiloxanes containing siloxane unitsrepresented by the wherein R, R and R" have the same meanings as definedwithin claim 2; Y is a member selected from the group consisting ofalkyl and aryl radicals; and b is an integer having a value from 0 to 2;and at least one other siloxane unit represented by the formula:

wherein W and W are hydrocarbon radicals; and e is an integer having avalue of from 0 to 2.

9. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is delta-aminobutylmethylsiloxane.

10. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is a copolymeric siloxane containing trimethylsiloxyend-blocked dimethylsiloxane and delta-aminobutylmethylsiloxy groups.

11. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is N-beta-cyanoethyldelta-aminobutylmethylpolysiloxane.

12. The process as claimed in claim 2, wherein the aminoalkyl siliconedye-fixative is a crude hydrolyzate ofdelta-aminobutylmethylpolysiloxane.

13-. The process as claimed in claim 2, wherein the dye-fixative is acopper coordinated complex of an aminoalkyl silicone of the classdescribed.

14. The process as claimed in claim 2, wherein the dye-fixative is achromium coordinated complex of an aminoalkyl silicone of the classdescribed.

15. The process as claimed in claim 2, wherein said dye-fixative isdeposited on the substrate from aqueous solution.

16. The process as claimed in claim 2, wherein said dye-fixative isdeposited on the substrate from an alcoholic solution.

17. The process as claimed in claim 2, wherein said dye-fixative isdeposited on the substrate from an aqueous solution containing amonobasic organic acid.

18. The process as claimed in claim 2, wherein said dye-fixative isdeposited on the substrate from a solution consisting of approximatelyequal parts of water and isopropanol and containing a small amount ofacetic acid.

References Cited UNITED STATES PATENTS DONA-LD LEVY, Primary ExaminerUS. Cl. X.R. 8-165 UljIITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3, 741, 721 Dated Ju e 26, 1973 11Qmenick D Ga li-It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

The term of this pate t subsque t. to December 8, 1987, has

bee disclaimed.

Signed and Scaled this Twenty-eighth Day Of September 1976 [SEAL]Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nj'laremsand Trademarks

